Photographic developers comprising bis-(di-hydroxyalkyl aminomethyl)-hydroquinones



Patented July 22, 1952 PHOTOGRAPHIC DEVELOPERS COMPRISING BIS- (DIHYDROXYALKYL AMINOMETIL. YL) -HYDROQUINON ES Thomas S. Donovan andFrederic R. Bean, Rochester, N. Y., assignors to Eastman Kodak Company,Rochester, N.

Jersey Y., a corporation of New 'No Drawing. Application July 7,1949,

Serial No. 103,532

This invention relatesto photographic developers and-more particularlyto photographic developing solutions.

Prominent among the developing agents now 'empolyed in the rapiddevelopment of 'photographic images are those comprising hydroquinoneand Elon (p -N-methylaminophenol). While various formulas of thesedevelopers are excellently suited for general" photographic use, theyhave notbeen outstanding where developers: ofincreased water solubilityare: required. 7

For example, certain aqueous photographic developer solutions comprisinghydroquinone and Elon, give rise. to the formation of a precipitateafter-the solutions have been allowed to stand for-a time. s

Photographic developers which possess this desired water solubilitywould represent a substantial advance in the art, if such developersretained muchof the developing activity exercised byr hydroquinone.

It is, therefore, an object of our invention to provide photographicdevelopers which possess Water solubility of a high degree. A furtherobject is to provide photographic developerswhich, in addition to havinga high degree of water solubility, have suflicient developing activity(ability to reduce silver halide) to warrant their use in developingsolutions. Other objects will become apparent from the followingdescription and examples.

According to our invention we accomplish the above objects by providingphotographic developer solutions comprising a bis-[di-(hydroxyalkyl)aminomethyl] hydroquinone.

The bis- [di- (hydroxyalkyl) aminomethyllhydroquinones useful inpracticing our invention can advantageously be represented by thefollowing general formula:

wherein R and R1 each represents a hydroxyalkyl group containing from 2to 3 carbon atoms, Compounds represented by the, above formula whichhave been. found to' be especially 12 Claims.

useful for the purposes of our invention include those represented bythe following formulas:

I CHiCHr-OH $Hs HO-CHCH:

NCH

HO-CHCH I OH. CH: 1

2,=-bis-[di- (B-hydroxyisopropyl) aminomethyl hydroqumone on I l omcnlcmon *CHr-N photographic developer formula useful in prac-' ticing ourinvention:

EXAMPLEI Elon ('p-(N methylarnino) phenol) grams 2.5 2,5-bis- [di(flhydroxyethyl) aminomethyl] hydroquinone oxalate grams 2.5

Sodium sulfite (anhydrous) do 75.0 Sodium carbonate (anhydrous) do 25.0Potassium bromide do 1.5 Water to liters 1.0

This developer solution was used to develop 5'0 motion-picturepositive-film;

The compounds represented j' by the above 3 EXAMPLEZ Another formulawhich has been found useful in practicing our invention is:

2,5-bis- [di- (flhydroxyethyl) aminomethyll hydroquinone oxlate grams5.0 Sodium sulfite (anhydrous) do 75.0 Sodium carbonate (anhydrous) do25.0 Potassium 'bromide i do 1.5 Water to; i liters 1.0

Photographic developer formulas other than those illustrated above canbeemployed to advantage. Both the amount and type of hydroquininedeveloping agent can be varied to suit the requirements of the operator.The above formulas are merely illustrative'and are'not intended to limitour invention. I

The developing agents represented: by the above general formula areespecially useful in the preparation of concentrated .photographic Wdeveloper formulas which find use in the field of The developers comingX-ray photography. within the scope of the present invention arecharacterized by their excellent solubility in water, a property whichis much desired for such concentrated photographic. formulas. Whereasthe conventional I-IQ-MQ (hydroquinone-Elon) concentrated developersolutions give rise to precipitates on standing, the developer solutionsof the present invention donot show a precipitate at even higherconcentrations. Typical concentrated developer formulas in which thehydroquinone compounds of our invention can be used includethoseillustrated in the application of F. R. Bean; 'Serial'No. 94,510,'filedMay 20, 1949, now U. S. Patent 2,578,281, issued December 11,. 1951.Such solutions generally comprise from about 50 to '75 grams of phenolicdeveloper per liter of solution, although many of the hydroquinonecompounds of, our invention permit even higher concentrations ofphenolic developers to be used. The hydroquinone compounds representedby the above general formula can also be usedin tanning developersolutions, although usually less efiicaciously than hydroquinone itself,we have found.

The'following examples illustrate the method of preparation of typicalhydroquinone compounds coming within the scope of our invention.

EXAMPLE 3 2,5 bisldi- (fi-hydhozyeth'ylamz'no) ethyl] hydroquinoneoxalate 55 g. of hydroquinonewere dissolved in 125 cc. of water and 105g'. of diethanolamine were added. The solution-was cooled-to C., 87 cc.of a 37 per cent formalin solution were added dropwise with stirringover a period of 30 minutes, and the solution was then stirred at roomtemperature for an additional hour. The reaction mixture wasconcentrated under. a vacuum to a thin syrup, 500 cc. of acetone added,and the acetone solution made acid to Congo Red with oxalic acid. Theproduct crystallized as fine, white prisms melting at 196197 C. (withdecomposition) They were very soluble in water.

2,5-bis Edi-(13 hydroxyisopropyl) aminom ethyll hydroquinone a 28 g. ofhydroquinone were dissolved in 125 cc.

of a 75% solution of ethyl alcohol, and-7'7 g. of diisopropanolaminewere added. "The solution was cooled to 15 C,., and 44 cc. of 37 percent formalin were added dropwise with stirring. The mixture was thenwarmed on a steam bath for 30 minutes and the alcohol removed byevaporation. Thesyrupy residue was taken up in 150 cc. of water, thesolution treated with decolorizing carbon and filtered. From thefiltrate, on standing, there separated a tan crystalline solid whichwasrecrystalizd' from ethanol. The crystals melted at 180-'182 (landwere soluble in water, acids, alkalies, and alcohol. They wereessentially insoluble in ether or benzene.

-- Other hydroquinone compounds useful in practicing our invention canbe prepared by interacting hydroquinone, formaldehyde and otherhydroalkylamines in the manner described above. The hydroquinonecompounds of our invention can be mixed with the usual strongly alkalinev ber, resins, etc.

'materials employed in photographic developer solutions to give a drymixture, and this mixture can then be dissolved in water to give asolution useful in preparing the desired developing formulas, i. e. theusual constituents employed in photographic formulas can then be added.The ratio of materials added to the mixture correspond to those given inthe above formulas, although other known ratios of developing agent toalkali can be used to advantage, as. set forth above, theparticular'ratios desired can be varied to suit the requirements of theoperator.

The bis-Edi (hydroxyalkyl) aminomethyllhydroguinones of our inventioncan also be used as oxidationinhibitorsj for gasoline, fatty oils, rub-They can also'be efiicaciously used'in processes for oxidatively dyeingwool or fur, e. g. in the former their dilute aqueous alkaline.solutions (or bysoaking the object to be dyed in an alcoholic solutionof the hydro wherein R and R1 represents a hydr'oxyalkyl group} f 2. Aphotographic silver halide developer solution comprising as the activedeveloping agent an acid addition salt of a compound selected from thoserepresented by the following general formula:

R om-N N-CHa R, DELL} wherein R and R1each representsa-hydroxalkyl groupcontaining from 2 to '3 'carbon'atoms.

3. A photographic silver halide developer solution comprising as theactive developing agent an acid addition salt of a compound selectedfrom those represented by the following general formula:

wherein R and R1 each represents a p-hydroxyalkyl group containing from2 to 3 carbon atoms.

4. A photographic silver halide developer solution comprising as theactive developing agent an acid addition salt of the compoundrepresented by the following formula:

HO-CHzCH1 CHaCHr-OH N-CH HO-CHzCHa 5. A photographic silver halidedeveloper solution comprising as the active developing agent an acidaddition salt of the compound represented by the following formula:

OH: OH

CHzCH-OH OH:

| CHg-N HO-CHCH;

OHaCH-OH N-CHz CHI HO-OHC 6. A photographic silver halide developersolution comprising as the active developing agent an acid addition saltof the compound represented by the following formula:

CHr-N N-CH HO-CHzCHzCHg 7. A solid mixture of chemicals useful forforming a photographic silver halide developer solution by dissolving inwater comprising as a developing agent an acid addition salt of acompound selected from those represented by the following generalformula:

CHz-N wherein R and R1 each represents a hydroxyalkyl group, and astrongly alkaline material.

8. A solid mixture of chemicals useful for forming a photographic silverhalide developer solu tion by dissolving in water comprising as adeveloping agent an acid addition salt of a compound selected from thoserepresented by the following general'formula:

wherein R and R1 each represents a hydroxyalkyl group containing from 2to 3 carbon atoms, and a strongly alkaline material.

9. A solid mixture of chemicals useful for forming a photographic silverhalide developer solution by dissolving in water comprising as adeveloping agent an acid addition salt of a compound selected from thoserepresented by the following general formula:

CH2--N/ o aCHa-OH CHr-N HO-CHzOHz and a strongly alkaline material.

11. A solid mixture of chemicals useful for forming a photographicsilver halide developer solution by dissolving in water comprising as adeveloping agent an acid addition salt of the compound represented bythe following formula:

CH2 H-OH CH: CH

HO-JJHCHa CHzCH-OH N--CH2 OH: H 0-030 2 0H Ha and a strongly alkalinematerial.

12. A solid mixture of chemicals useful for forming a photographicsilver halide developer solution by dissolving in water comprising as adeveloping agent an acid addition salt of the compound represented bythe following formula:

l CHgOHzCHg-OH HO-CHzCHzCHr N-CHa BIO-OHzCH OH;

and a strongly alkaline material.

THOMAS S. DONOVAN. FREDERIC R. BEAN.

(References on followingpage) 2,304,953 Peterson Dec.15, 1942 7; 8.;REFERENCES CITED V',OfI-I-IER ;EEFERENCES The following references areof record in the Henn'eyf a hd; Dufilefl- Handbook of Pho file of thispatent: tography, McGraw HilLNew York, 1939; pages- UNITED STATESPATENTS 5 328, 2 ,and 334 cited. r w 1 Number Name Date 2,163,166Wilmanns et a1 June 20, 1939

1. A PHOTOGRAPHIC SILVER HALIDE DEVELOPER SOLUTION COMPRISING AS THEACTIVE DEVELOPING AGENT AN ACID ADDITION SALT OF A COMPOUND SELECTEDFROM THOSE REPRESENTED BY THE FOLLOWING GENERAL FORMULA: